Madhrasathul Ahmadhiya Department Of Chemistry

SEMESTER-III UNIT:4

CHEMICAL KINETICS

1. Define the following:

i). Rate of the reaction:………………………………………………………………………………………

………………………………………………………………………………………………………………..

ii). Order of the reaction:…………………………………………………………………………………….

………………………………………………………………………………………………………………..

iii). Over all order of the reaction:…………………………………………………………………………...

………………………………………………………………………………………………………………..

2. For each of the following reactions, decide which method/s (there may be more than one method) you
could use monitor the progress.

a). CaCO3(s) + 2 HCl(aq) 2CaCl2(aq) + CO2(g) + H2O(l)

………………………………………………………………………………………………………………..

b). MnO4-(aq) + 5C2O42-(aq) + 16H+ 2Mn2+(aq) + 8H2O(l) + 10CO2(g)

………………………………………………………………………………………………………………..

c). CH3CHBrCH2CH3 + NaOH CH3CH(OH)CH2CH3 + NaBr

………………………………………………………………………………………………………………..

3. Hydrogen reacts with iodine at 450OC to give hydrogen iodide. The results from several experiments
designed to find the rate of reaction are given below:

Experiment Initial[I2] moldm-3 Initial[H2] moldm-3 Initial rate moldm-3s-1

1 0.001 0.001 1

2 0.003 0.001 3

3 0.001 0.004 4

i). Find the order of the reaction with respect to each of the reactants.

r d
1|Page Grade 12-3 semester-2013
Madhrasathul Ahmadhiya Department Of Chemistry

ii). Write the rate equation for the reaction………………………………………………………………….

iii). Explain why the rate equation cannot be written from the stochiometric (chemical) equation for the
reaction, but must be found experimentally.

………………………………………………………………………………………………………………..

………………………………………………………………………………………………………………..

………………………………………………………………………………………………………………..

4. The reaction of ethanoic anhydride (CH3CO)2O, with ethanol, C2H5OH, can be represented by the
equation:

(CH3CO)2O(aq) + C2H5OH(aq) CH3CO2C2H5(aq) + CH3CO2H(aq)

Run [(CH3CO)2O] [C2H5OH] Initial rate

/moldm-3 /moldm-3 /moldm-3s-1
1 0.400 0.200 6.60 x 10-4

2 0.400 0.400 1.32 x 10-3

3 0.800 0.400 2.64 x 10-3

i). State and explain the order of the reaction with respect to each reactant.

 With respct to (CH3CO)2O:………………………………………………………………………...

……………………………………………………………………………………………………………….

 With respect to C2H5OH:…………………………………………………………………………..

………………………………………………………………………………………………………………

ii). Write an expression for the rate equation:……………………………………………………………….

iii). What is the overall order of the reaction:……………………………………………………………….

iv). Calculate the value, with units, for the rate constant.

r d
2|Page Grade 12-3 semester-2013
Madhrasathul Ahmadhiya Department Of Chemistry

5. The oxidation of nitrogen monoxide to nitrogen dioxide in car exhausts involve carbon monoxide and
oxygen.

NO(g) + CO(g) + O2(g) NO2(g) + CO2(g)

The rate of this reaction can be followed colorimetrically because NO 2(g) is colored.

a). (i) Using the axes,to show the concentration of NO2(g) produced varies with time.

ii) Show with reference to your sketch, how the initial rate of reaction could be deduced.

………………………………………………………………………………………………………………..

………………………………………………………………………………………………………………..

b) The results from a series of experiments are shown below:

[NO2(g)] [CO(g)] [O2(g)] Initial rate

Run /moldm-3 /moldm-3 /moldm-3 /moldm-3s-1
x10-3 x10-3 x10-3

1 1.00 1.00 1.00 4.40x10-4

2 2.00 1.00 1.00 1.76x10-3

3 2.00 2.00 1.00 1.76x10-3

4 4.00 1.00 2.00 7.04x10-3

i) Deduce the order of the reaction with respect to NO(g). Show your reasoning.

r d
3|Page Grade 12-3 semester-2013
Madhrasathul Ahmadhiya Department Of Chemistry

ii) State the order of the reaction with respect to CO(g) and O2(g).

 For CO(g):

 For O2(g):

iii) Write an expression for the rate equation:………………………………………………………………

iv) Calculate a value for the rate constant. State the unit of k.

6. Substitution reactions of halogenoalkanes can proceed via an SN1 or SN2 mechanism. When

1-bromobutane, 2-bromobutane and 2-bromo-2-methylpropane are reacted separately with aqueous

sodium hydroxide solution each gives the corresponding alcohol.

i) Give the mechanism for SN1 and SN2 reaction between 2-bromobutane and hydroxide ion.

SN1 mechanism:

SN2 mechanism:

ii) Explain the optical activity in both of the above mechanisms.

………………………………………………………………………………………………………………..

………………………………………………………………………………………………………………..

r d
4|Page Grade 12-3 semester-2013
Madhrasathul Ahmadhiya Department Of Chemistry

………………………………………………………………………………………………………………..

……………………………………………………………………………………………………………….

7.

r d
5|Page Grade 12-3 semester-2013
Madhrasathul Ahmadhiya Department Of Chemistry

r d
6|Page Grade 12-3 semester-2013
Madhrasathul Ahmadhiya Department Of Chemistry

r d
7|Page Grade 12-3 semester-2013
Madhrasathul Ahmadhiya Department Of Chemistry

8.

r d
8|Page Grade 12-3 semester-2013
Madhrasathul Ahmadhiya Department Of Chemistry

r d
9|Page Grade 12-3 semester-2013
Madhrasathul Ahmadhiya Department Of Chemistry

r d
10 | P a g e Grade 12-3 semester-2013
Madhrasathul Ahmadhiya Department Of Chemistry

9.

r d
11 | P a g e Grade 12-3 semester-2013
Madhrasathul Ahmadhiya Department Of Chemistry

January 2010 unit 4 Qn . 23

1. Iodine and propanone react in the presence of an aqueous acid catalyst as follows

CH3COCH3 + I2 → CH3COCH2I + HI

To determine the rate equation for the reaction, propanone is reacted with iodine in the presence of
aqueous hydrochloric acid at constant temperature. Samples are withdrawn at known times, quenched
with sodium hydrogencarbonate solution, and the iodine remaining titrated with a standard solution of
sodium thiosulfate.

The rate equation for the reaction is

rate = k[CH3COCH3]1 [H+]1 [I2]0

(a) The graph of [I2] against time is a straight line, showing that the order of reaction with respect to
iodine is zero.

(i) Explain why the propanone and the hydrogen ions must be in large excess in this experiment in order
to give this straight line. (2)

(ii) What further experiment could be done to show that the order of reaction with respect to propanone is
one? State the effect of this change on the graph.(2)
r d
12 | P a g e Grade 12-3 semester-2013
Madhrasathul Ahmadhiya Department Of Chemistry

(iii) Explain why the minimum number of steps in the mechanism for this reaction is two.(2)

(b) Sodium hydrogencarbonate stops the reaction by neutralizing the acid catalyst.

(i) Give the ionic equation for the reaction between sodium hydrogencarbonate and acid.(1)

(ii) Sodium hydroxide cannot be used for neutralization because under very alkaline conditions a reaction
occurs between propanone and iodine.

Write the equation for this reaction. State symbols are not required.(3)

June 2010 unit 4 Qn. 17

2.A bromoalkane has the molecular formula C4H9Br. The ionic equation for the hydrolysis of this
compound with aqueous sodium hydroxide is shown below.

C4H9Br + OH– → C4H9OH + Br–

(a) The rate of hydrolysis was investigated by mixing a large excess of the bromoalkane with aqueous
sodium hydroxide, and measuring the time taken for all the hydroxide ions to be used up. This was
carried out with different initial concentrations of the bromoalkane and the hydroxide ions. The results
are shown in the table below.

(i) Complete the missing value of the initial rate in the table.(1)

(ii) State the order of the reaction with respect to C4H9Br and to OH–. Justify each answer by reference
to the concentrations of both reactants.(3)

Order with respect to C4H9Br.........................................................................................................................

Reason .............................................................................................................................. .............................

Order with respect to OH– ..............................................................................................................................

Reason .............................................................................................................................. .............................

(iii) Deduce the rate equation for the reaction.(1)

r d
13 | P a g e Grade 12-3 semester-2013
Madhrasathul Ahmadhiya Department Of Chemistry

Rate = .............................................................................................................................. ..............................

(iv) Use the results for the first experiment in the table to calculate the rate constant and give its units.(2)

Units .............................................................................................................................. ................................

(b) What evidence supports the theory that there is more than one step in the reaction mechanism? (1)

(c) Write the mechanism for the hydrolysis of C4H9Br which is consistent with your rate equation. Show
the structure of C4H9Br clearly in your mechanism.(3)

*(d) Explain why primary and tertiary bromoalkanes are hydrolysed by different mechanisms.(2)

January 2011 unit 4 Qn.19

3.A student investigated the reaction between iodine and propanone in acidic conditions.

CH3COCH3(aq) + I2(aq) → CH3COCH2I(aq) + HI(aq)

 50 cm3 of 0.020 mol dm–3 iodine solution was measured into a flask.
 25 cm3of propanone and 25 cm3of 1.0 mol dm–3sulfuric acid were measured into a

second flask.

 Several 10 cm3samples of 0.5 mol dm–3sodium hydrogencarbonate solution were placed in

separate conical flasks.
 The mixture of propanone and sulfuric acid was added to the iodine, and a clock started.
 At two minute intervals, 10 cm3 of the reaction mixture was removed and added to one of the
flasks containing sodium hydrogencarbonate solution.
 The contents of this flask were then titrated with 0.01 mol dm–3sodium thiosulfate.

(a) Explain the purpose of adding the reaction mixture to the sodium hydrogencarbonate.(2)

(b) What indicator should be used in the titration?(1)

*(c) In this experiment the concentration of the iodine was 0.020 mol dm –3 and the concentrations of
propanone and sulfuric acid were both 1.00 mol dm–3. Why was the iodine solution used much less
concentrated than the propanone and sulfuric acid?(2)

(d) The shape of the graph obtained from the results of the experiment is shown below.

r d
14 | P a g e Grade 12-3 semester-2013
Madhrasathul Ahmadhiya Department Of Chemistry

Use the graph to deduce the order of reaction with respect to iodine, explaining your reasoning.(2)

(e) The solutions used in this experiment could be measured using either measuring cylinders or pipettes.

Give one advantage of using a measuring cylinder and one advantage of using a pipette.(2)

(f) In a further investigation, different volumes of sulfuric acid, propanone, iodine and water were mixed.
The time taken for the mixture to go colourless was measured.

The experiments were repeated and the results below show average values for the rate of the reaction.

(i) Explain why water is added in experiments 2 and 3.(1)

(ii) Show how you would use the data in the table to deduce the order of reaction with respect to
propanone and hydrogen ions. Write the rate equation for the reaction.(3)

r d
15 | P a g e Grade 12-3 semester-2013
Madhrasathul Ahmadhiya Department Of Chemistry

4.

r d
16 | P a g e Grade 12-3 semester-2013
Madhrasathul Ahmadhiya Department Of Chemistry

r d
17 | P a g e Grade 12-3 semester-2013